Highly thermally stable three-dimensional spongelike mesoporous CexZr1-xO2 solid solutions consisting of nanometer size particles with different Ce/Zr compositions were synthesized by a modified sol-gel procedure using a triethanolamine/water mixture as a solvent to be used in liquid Knoevenagel condensation reaction. These materials were investigated in detail by means of X-ray diffraction (XRD), Raman spectroscopy, chemical analysis, X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), UV-Vis spectroscopy, Fourier transform infrared spectroscopy (FT-IR) and adsorption microcalorimetry. The XRD, HRTEM and XPS studies proved the presence of nanocrystalline CexZr1-xO2 solid solutions. These solid solutions showed excellent chemoselectivity in the classical Knoevenagel reaction. The large pore sizes (around 10 nm) highlight the possibility of using CexZr1-xO2 as a support material for versatile catalytic systems. The results obtained from NH3 and SO2 adsorption microcalorimetry experiments successfully demonstrated the incorporation of ZrO2 into the CeO2 lattice resulting in both acidic and basic surface sites in a mixed oxide matrix. (c) 2009 Elsevier Inc. All rights reserved.